JP6888896B2 - Catalytic chlorination of 3,3,3-trifluoropropene to 2,3-dichloro-1,1,1-trifluoropropane - Google Patents

Description

The present invention relates to a process for producing 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) by chlorinating 3,3,3-trifluoro-1-propene (HFO-1243zf). ..

Over the past few decades, many manufacturing industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFC and HCFC have been widely used. Its use is aerosol propellants, refrigerants, detergents; swelling agents for thermoplastics and thermosetting foams; heat transfer media, gaseous dielectric materials; digestive and fire extinguishing agents; power cycle working fluids, polymerization media, fine particle removal Includes fluids, dispersion medium fluids, buffing abrasive agents, and replacement dryers. In the search for alternatives to these versatile compounds, many manufacturers have turned their attention to the use of hydrofluorocarbons (HFCs).

Although the HFC does not contribute to the destruction of stratospheric ozone, it is a concern because it contributes to the "greenhouse effect". That is, HFCs contribute to global warming. As a result of contributing to global warming, HFCs will be the subject of further investigation and their widespread use will also be constrained in the future. Therefore, there is a demand for chemical compounds that combine low ozone depletion potential (ODP) and low global warming potential (GWP).

One of the beneficial compounds with such a low GWP is 2,3,3,3-tetrafluoro-1-propen (HFO-1234yf). This compound is useful as a refrigerant and a foaming agent. This compound is produced in many ways, one of which is derived from the following process.

(1) In a gas phase reactor filled with a solid catalyst
_{(CX 2 = CCl-CH 2} X or CX ₃ -CCl = CH ₂ or _{CX 3 -CHCl-CH 2 X)} + HF ->
2-Chloro-3,3,3-trifluoropropene (HCFO-1233xf) + HCl
(2) In a liquid phase reactor filled with a liquid hydrofluorination catalyst
2-Chloro-3,3,3-trifluoropropene (HCFO-1233xf) + HF->
2-Chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb)
(3) In the gas phase reactor
2-Chloro-1,1,1,2-Tetrafluoropropane (HCFC-244bb)->
2,3,3,3-Tetrafluoropropene (HFO-1234yf)
Thus, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) is an intermediate in the process of producing 2,3,3,3-tetrafluoropropene (HFO-1234yf). HCFC-1233xf is obtained by dehydrochlorination of HCFC-243db, which is a product of the process of the present application.

U.S. Patent Application Publication No. 2011/0118513

So far, there have been various methods for producing HCFC-243db. For example, chlorination of 3,3,3-trifluoro-1-propene (HFO-1243zf) is carried out using ultraviolet light, at high temperatures, or in a catalyst-free liquid phase. However, there are many problems associated with these methods. The UV light approach is less selective and difficult to scale up to a commercial process. In addition, the reaction in the uncatalyzed liquid phase is very slow and needs to be carried out at a high temperature. However, even under these conditions tar is also formed.

Therefore, in this technique, there is a need for a new process for manufacturing HCFC-243db, which does not have the drawbacks of the prior art. The invention of the present application overcomes these problems.

The process of the present application relates to the process of preparing 1,1,1-trifluoro-2,3-dichloropropane, which involves contacting 3,3,3-trifluoropropene with chlorine in the presence of a catalyst 1, It comprises the step of forming 1,1-trifluoro-2,3-dichloropropane, the catalyst containing at least one metal halide, the metal being an element of Group 13, 14 or 15 of the Periodic Table. There are, or transition metals, or a combination thereof. This reaction can be carried out in both the gas phase and the liquid phase.

The process produces 1,1,1-trifluoro-2,3-dichloropropane with excellent yield and high selectivity.

The following figure further illustrates the invention of the present application in a non-limiting manner.
In FIG. 1, the selectivity of 243db by chlorination of 1243zf using the catalyst shown below is compared using a graph. The catalysts used were activated carbon (Comparative Example 1), 15% CrCl ₃ / C (Example 1), 5% FeCl ₃ / C (Example 3), and 5% CrCl ₃ / C (Example 6). .. In FIG. 2, the results of the process of the present application are compared with the reaction carried out at high temperature and without catalyst using a graph as a function of pressure and time. The lower plot graphically represents the change in pressure as a function of time for the product formed according to the procedure of Example 11. The middle plot graphically represents the change in pressure as a function of time for the product formed according to the procedure of Comparative Example 2. The upper plot graphically represents the change in pressure as a function of time for the product formed according to the procedure of Comparative Example 3.

In the present specification, "includes" ("comprises", "comprising"), "includes (as a part of the whole)" ("includes", "including"), "has" ("has", "having"). , Or any other variant of these, is intended to include non-exclusive inclusion. For example, a process, method, article or device that includes an enumerated element is not necessarily limited to these elements, but to other elements that are not explicitly enumerated, or to such a process, method, article or device. It may contain other unique elements. Moreover, unless explicitly stated, "or" ("or") is an inclusive "or", not an exclusionary "or". For example, the condition A or B is satisfied by any one of the following cases. That is, when A is true (or present) and B is false (or non-existent), when A is false (or non-existent) and B is true (or present), and both A and B. Is true (or exists).

Also, the use of "one" ("a", "an") is employed to describe the elements and components described herein. This is done solely for convenience and to give a general scope of the scope of the invention. This statement should be construed as one or at least one, and the singular also includes more than one, unless it is clear that it means something else.

When representing a numerical range, another embodiment includes from the one particular number and / or to the other particular number. Similarly, when a number is approximated by the use of the antecedent "about", it is understood that a particular number forms another embodiment. All ranges are inclusive and associative. In addition, the numerical references given in the range include any number in the range.

Unless otherwise defined, all scientific and technological terms used herein have the same meaning as commonly understood by one of ordinary skill in the art in the art to which the present invention belongs. Methods and materials similar to or equivalent to the methods and materials described herein can be used in the practice and testing of embodiments of the present invention. However, the appropriate methods and materials are described below. All publications, patent applications, patents, and other references referred to herein are incorporated by reference in their entirety, unless specific parts are cited. If there is a dispute, this specification regulates it, including the definition. Moreover, the materials, methods and examples are for explanatory purposes only and are not intended to be restrictive.

Although many embodiments and embodiments are described herein, they are merely exemplary and not restrictive. Those skilled in the art who have read this specification will appreciate that other embodiments and embodiments are possible without departing from the scope of the present invention. The features and benefits of any one or more embodiments will be apparent from the detailed description and claims below.

As described above, the process of the present application relates to the process of chlorinating 3,3,3-trifluoropropene in the presence of a catalyst to form 1,1,1-trifluoro-2,3-dichloropropane. It contains at least one metal halide, and the metal is a metal of Group 13, 14 or 15 of the Periodic Table, or a transition metal.

As used herein, the term "halide" means fluoride, chloride, bromide and iodide.

The term metal, as used herein, means metal in the periodic table. Non-metals, halogens, noble gases and actinides are excluded. However, as used herein, metal terms include metalloids. Examples of metals include metals of Groups 13 and 14 of the Periodic Table. The term also includes transition metals as defined herein. Examples of metals are nickel, chromium, iron, scandium, ittrium, lantern, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, renium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, antimony, aluminum. , Tin, and lead. It should be noted that antimony is a metalloid, as defined herein, and is a metal according to the definition herein.

The term "transition metal" means elements of groups 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, including lanthanides. Examples of transition metals include nickel, chromium, iron, scandium, ittrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, renium, ruthenium, osmium, cobalt, palladium, copper, zinc, and tantalum. included.

Since the catalyst used in the chlorination reaction described herein is in the form of a metal halide, the metal used herein depends on the metal forming the salt with the halide, +1. It has a positive oxidation number of +2, +3, +4 or +5.

The term "activated carbon" refers to any carbon having a relatively large surface area, ^{such as about 50 to about 3000 m 2} or about 100 to about 2000 m ² (eg, about 200 to about 1500 m ² or about 300 to about 1000 m ^2). including. Activated carbon can be obtained from any carbonaceous material, such as coal (eg charcoal), nut shells (eg coconut) and wood. Any form of activated carbon, such as powder, granules, and pellets, may be used. Modified with Cr, Mn, Au, Fe, Sn, Ta, Ti, Sb, Al, Co, Ni, Mo, Ru, Rh, Pd and / or Pt and / or one or more compounds of these metals (eg, halides). Activated carbon (eg, impregnated) may be used.

In some embodiments, the activated carbon is washed with at least one basic solution to remove the silicate. For example, activated carbon is washed with alkali metal hydroxides, alkaline earth metal hydroxides or ammonium hydroxide. Examples of basic solutions that have been used to wash activated carbon include sodium hydroxide, ammonium hydroxide, potassium hydroxide and the like.

Furthermore, other suitable forms of activated carbon include, but are not limited to, acid-washed activated carbon powder produced by steam activation of lignite. In some embodiments, organic and / or inorganic nitrogen-containing acids such as nitric acid are used. Additional acids that can be used include, but are not limited to, sulfuric acid, hydrochloric acid, phosphoric acid and combinations thereof. The acid preferably has an aqueous solution concentration of 2-12 mol / L. According to one embodiment, the activated carbon is soaked for at least 1 hour, eg 1-36 hours, or 1-10 hours. Optionally, the activated carbon may be agitated during immersion. If necessary, the activated carbon is washed and then rinsed with deionized water to increase the pH to 5-8. In some embodiments, washing with at least one acid and at least one base reduces calcined ash and removes silicates.

The metals in the metal halides used as catalysts are the metals of Groups 13 and 14 of the Periodic Table, transition metals and metalloids Antimon. Examples of metals include nickel, chromium, iron, scandium, ittrium, lantern, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, renium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, aluminum, Includes tin and lead. It should be noted that antimony is a metalloid, as defined herein. However, as defined herein, metalloids are included in the definition of metals. Examples of metal halides are nickel halide, chromium halide, iron halide, scandium halide, yttrium halide, lanthanum halide, titanium halide, zirconium halide, hafnium halide, vanadium halide, molybdenum halide. , Tungsten halide, manganese halide, renium halide, ruthenium halide, osmium halide, cobalt halide, palladium halide, copper halide, zinc halide, antimonate halide, tantalum halide, aluminum halide, halogen Includes tin and lead halides. In one embodiment, the metal halide is nickel halide, iron halide, chromium halide, or a combination thereof and is used as a catalyst with or without carrying on activated carbon. To. In another embodiment, the metal halide is bromide or chloride. In yet another embodiment, the halide is chloride. In another embodiment, the metal halide is nickel chloride, iron chloride, or chromium chloride or a combination thereof.

The metal halide that is the catalyst of the chlorination process of the present application may not be supported on the activated carbon, or may be supported on the activated carbon. The activated carbon may be a non-cleaned product, or may be an acid-washed product or a base-washed product.

In the chlorination reaction, chlorine exists in a gaseous state. Chlorine gas may be used, or chlorine gas may be generated in situ from the reaction of gaseous hydrogen chloride with oxygen.
In one embodiment, the chlorination reaction is carried out in the absence of water. If water is present, it is present in less than 1% by weight in one embodiment and less than 0.5% by weight in another embodiment.

3,3,3-Trifluoropropene is commercially available. As an alternative method, it can be prepared using a technique known in the art. For example, Patent Document 1 can be referred to, the contents of which are incorporated by reference.

As described below, the chlorination reaction can be carried out in either the gas phase or the liquid phase.

If carried out in the gas phase, the process is carried out at an effective temperature and pressure. In one embodiment, the reaction is carried out at a temperature in the range of about 80 to about 200 ° C. In another embodiment, the reaction is carried out at a temperature in the range of 80 to about 160 ° C. In yet another embodiment, the chlorination reaction is carried out at a temperature in the range of about 80 to about 130 ° C. and in another embodiment in the range of about 80 to about 120 ° C. The process can be carried out at pressures ranging from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa). In another embodiment, the pressure range is in the range of about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment, the pressure range is about 20 psig (239.2 kPa). It ranges from ~ about 50 psig (446.1 kPa). Thus, in one embodiment, the process is at a temperature in the gas phase in the range of about 80 to about 200 ° C. and from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), another embodiment. In another embodiment, from about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), in another embodiment, from about 10 psig (170.3 kPa) to about 50 psig (446.1 kPa), for example, about 20 psig ( It is carried out at a pressure in the range of 239.2 kPa) to about 50 psig (446.1 kPa). In another embodiment, the chlorination reaction is at a temperature in the range of about 80 to about 160 ° C. and from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment. Pressures ranging from about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa) and, in another embodiment, from about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). In a further embodiment, the chlorination reaction is at a temperature in the range of about 80-130 ° C. and from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment about 1 atm. Pressures ranging from (101.3 kPa) to about 50 psig (446.1 kPa) and, in another embodiment, from about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa).

The 3,3,3-trifluoropropene and chlorine gas are present in an effective amount that causes a chlorination reaction. The molar amount of 3,3,3-trifluoropropene is present in excess of the molar amount of chlorine gas in one embodiment. In one embodiment, the molar ratio of 3,3,3-trifluoropropene to chlorine gas is in the range of about 1: 0.02 to about 1: 1. In another embodiment, the molar ratio of 3,3,3-trifluoropropene to chlorine gas is in the range of about 1: 0.1 to about 1: 0.8. In yet another embodiment, the molar ratio of 3,3,3-trifluoropropene to chlorine gas is in the range of about 1: 0.1 to about 1: 0.5.

The contact time of the chlorination reaction, that is, the time for causing the reaction, can be in the range of about 0.1 seconds to about 120 seconds, and in another embodiment about 5 seconds to about 1 minute. However, longer or shorter times can be used. The contact time used in this specification is expressed by the following formula:
Contact time (seconds) =
1 / ((total gas flow (SCCM) / 60 / catalyst volume)) x (14.7 + P (PSIG)) / 14.7x (298 / (273 + T (℃)))
Is determined by. Here, SCCM is the standard cubic centimeter per minute, P is the pressure, and PSIG is the gauge pressure, which is the working pressure in pounds per square inch, not the absolute pressure. T (° C) is the temperature in degrees Celsius and the catalyst volume is in cubic centimeters.

The metal halide catalyst is present in the gas phase in an effective amount of the catalyst in the chlorination reaction. In one embodiment, the catalyst is supported on activated carbon, which is an unwashed product or an acid or base washed product. In one embodiment, the metal halide is supported on the activated carbon and is about 2 to about 30% by weight of the activated carbon, in another embodiment about 3 to about 25% by weight, and in another embodiment about 5 to about 5 to about. It is present in an amount in the range of 20% by weight.

In one embodiment, the chlorination reaction is carried out to achieve a conversion of about 50% or higher, preferably about 90% or higher. The conversion rate is the number of moles of reactants consumed (molar ratio of 3,3,3-trifluoropropene) to the number of moles of reactants supplied to the reactor (3,3,3-trifluoropropene). It is calculated by dividing by the molar ratio) and multiplying by 100. The selectivity of the obtained 1,1,1-trifluoro-2,3-dichloropropane is preferably 60% or more, more preferably 80% or more. The selectivity is calculated by dividing the number of moles of product formed (1,1,1-trifluoro-2,3-dichloropropane) by the number of moles of reactants consumed.

The process of the present application in the gas phase provides higher 243db selectivity than the activated carbon itself at high temperatures, such as 100-160 ° C, or about 120-about 200 ° C in another embodiment. Thus, in these temperature ranges, the chlorination reaction is performed separately from vacuum to about 100 psig (790.8 kPa), in another embodiment from about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa). In the form, the pressure can be in the range of about 10 psig (170.3 kPa) to about 50 psig (446.1 kPa). The process of the present application can operate the process with a higher back pressure beyond the dew point of 243db.

This chlorination reaction can be carried out in any reactor suitable for the gas phase chlorination reaction. In certain embodiments, the reactor comprises a material that is resistant to the corrosive effects of chlorine and catalysts, such as Hastelloy, Inconel, Monel and fluorine polymer lining materials. Has been done. The container is a fixed catalyst bed or a fluidized bed. If desired, an inert gas such as nitrogen or argon may be used in the reactor during operation.

In one embodiment, as described above, the catalyst during the gas phase reaction is supported on the activated carbon, and the activated carbon may be a non-washed product, or may be an acid-washed product or a base-washed product.

In another embodiment, the chlorination reaction takes place in the liquid phase. The process of the present application in the liquid phase can be carried out in any suitable device such as a static mixer, a tubular reactor or a stirred vapor-liquid disengagement vessel. In one embodiment, the apparatus described herein is one or more materials that are resistant to corrosion, such as stainless steel, especially austenite-type stainless steel; Monel ™ nickel-copper alloy, Hasteloy ( It is made of nickel-based alloys, and high nickel alloys such as Inconel ™ nickel-chromium alloys; and copper coated steels. The process of the present application can be carried out batchwise or continuously.

Vigorous vibration, agitation and / or agitation may be required to complete the reaction. The degree of stirring depends on the desired reaction rate, then the reaction rate depends on the shape of the reactor, the residence time, the structure of the stirrer and baffle, and the 3,3,3-trifluoropropene in the solvent. Depends on solubility. Therefore, the chlorination reaction in the liquid phase is carried out by stirring.

In the liquid phase, the chlorination reaction can be carried out with or without an inert solvent. In the inert solvent, the 3,3,3-trifluoropropene is soluble in the solvent, and the 3,3,3-trifluoropropene and the 1,1,1-trifluoro-2,3 are used. -A solvent that can be easily separated from dichloropropane. The term "inert" means that the solvent does not react with chlorine, 3,3,3-trifluoropropene or 1,1,1-trifluoro-2,3-dichloropropane under the reaction conditions. Suitable solvents include, for example, carbon tetrachloride, 1,1,2-trichloro-1,2,2-trifluoroethane, CF ₃ (CF ₂ ) _n CF ₃ represented by C _5-8 linear peroxide. Fluoroalkyl compounds (where n is an integer of 3-6, including both ends of the range); or perhalogenated compounds such as hexachloroacetone and 1,1,1-trifluoro-2,3-dichloropropane. included.

The amount of solvent used in the reaction in the chlorination step is not particularly limited as long as 3,3,3-trifluoropropene can be dissolved thereby. In one embodiment, the amount of solvent present is from about 1 to about 1000% by weight based on the raw material components (total amount of 3,3,3-trifluoropropene and chlorine), and in another embodiment from about 50 to. It is in the range of about 100% by mass.
The catalyst used herein may be heterogeneous or may contain 3,3,3-trifluoro-1-propene / 2,3-dichloro-1,1,1-trifluoropropane (1243zf / 243db). It may be partially dissolved in the liquid phase. In another embodiment, the catalyst is a homogeneous catalyst.

The reaction is carried out with an effective amount of chlorine gas and 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane. As in the gas phase reaction, the molar amount of 3,3,3-trifluoropropene is present in excess of the molar amount of chlorine gas in one embodiment. In one embodiment, the molar amount of 3,3,3-trifluoropropene relative to chlorine is in the range of about 1: 0.02 to about 1; 1, and in another embodiment it is about 1: 0.1. It is ~ 1: 0.9, and in another embodiment, it is in the range of about 1: 0.1 to about 1: 0.95.

The chlorination reaction takes place at an effective temperature. In one embodiment, the effective temperature is in the range of about 20 to about 200 ° C., while in another embodiment it is in the range of about 30 to about 110 ° C., and in another embodiment it is in the range of about 35 to about 90 ° C.

The pressure of the reactor during the liquid phase process is not definitive and is usually the self-generated pressure of the system at the reaction temperature in batch reactions.

In the liquid phase, the metal halide catalyst is present in a catalytically effective amount. In one embodiment, the catalyst is non-supporting. In one embodiment, the catalyst is in the range of about 0.1-10% by weight of the reactants (ie, the total amount of chlorine and 3,3,3-trifluoropropene), in another embodiment from about 0.5 to. It is present in an amount in the range of about 6% by weight, in another embodiment about 1 to about 4% by weight.

The reaction time of the chlorination reaction in the liquid phase may vary over a wide range. However, the reaction time will typically range from about 0.01 to about 100 hours, for example from about 0.5 hours to about 50 hours.

The chlorination reaction in both the liquid phase and the gas phase is preferably carried out so as to achieve a conversion rate of about 50% or more, preferably 90% or more. As mentioned above, the reaction is carried out in one embodiment when the molar amount of 3,3,3-trifluoropropene is equal to or greater than chlorine. The conversion rate is the number of moles of reactants consumed (molar ratio of 3,3,3-trifluoropropene) to the number of moles of reactants supplied to the reactor (3,3,3-trifluoropropene). It is calculated by dividing by the molar ratio) and multiplying by 100. The achieved selectivity of 1,1,1-trifluoro-2,3-dichloropropane is preferably about 60% or more, more preferably about 80% or more. The selectivity is calculated by dividing the number of moles of product formed (1,1,1-trifluoro-2,3-dichloropropane) by the number of moles of reactants consumed.

Whether the reaction is carried out in the gas phase or the liquid phase, 1,1,1-trifluoro-2,3-dichloropropane is isolated, i.e. separated and collected. The product containing 1,1,1-trifluoro-2,3-dichloropropane is removed from the reactor by techniques known in the art such as siphoning. In the case of the gas phase, the product is drained from the reactor and liquefied. Products containing 1,1,1-trifluoro-2,3-dichloropropane are purified by techniques known in the art such as distillation. The process of the present application, whether performed in the gas phase or in the liquid phase, is commercially available and can be easily scaled up for commercial production. In addition, the rate of chlorination reaction using the process described herein has traditionally been 1,1,1-trifluoro-2,3-dichloropropane (1,1,1-trifluoro-2,3-dichloropropane) by chlorinating 3,3,3-trifluoropropene. It has a faster reaction rate than the process used to make HCFC243db) and offers higher conversion and selectivity.

There are several side reactions that antagonize the formation of 2,3-dichloro-1,1,1-trifluoropropane product (HCFC243db) in both gas and liquid phase chlorination reactions. These side reactions include:

a. Conversion of 243db to 1,1,1-trifluoro-3-chloropropylene
CF ₃ CHClCH ₂ Cl-> CF ₃ CCl = CH ₂ + CF ₃ CH = CHCl + HCl
243db 1233xf 1233zd
b. Conversion of 1233xf to 233ab
CF ₃ CCl = CH ₂ + Cl _2- > CF ₃ CCl ₂ CH ₂ Cl
1233xf 233ab
c. Conversion of 233da of 1233zd
CF ₃ CH = CClH + Cl _2- > CF ₃ CHCl-CHCl ₂
1233zd 233da
d. Formation of 1223xd
CF ₃ CCl ₂ CH ₂ Cl + CF ₃ CHClCHCl _2- > CF ₃ CCl = CHCl + HCl
233ab 233da 1223xd
e. Formation of 223aa from 1223xd
CF ₃ CCl = CHCl + Cl _2- > CF ₃ CCl ₂ CHCl ₂
1223xd 223aa
f. Conversion of 1213xa of 223aa
CF ₃ CCl ₂ CHCl _2- > CF ₃ CCl = CCl ₂ + HCl
223aa 1213xa
g. Conversion of 1213xa to 213ab
CF ₃ CCl = CCl ₂ + Cl _2- > CF ₃ CCl ₂ CCl ₃
1213xa 213ab
h. Converting 243db to 244db and 242dc
_{CF 3 CHClCH 2 Cl -> CF} 3 CHClCH 2 F + CF 2 ClCHClCH 2 Cl
243db 244db 242dc
Further, although not present in the gas phase, there is a risk of oligomerization and formation of black tar in the liquid phase chlorination reaction.

However, despite all these side reactions, the selectivity and conversion by using the process of the present application is surprisingly high.

Furthermore, the formation of the product can be confirmed by installing an analyzer such as gas chromatography on the reactor and performing continuous measurements.

In one embodiment, anhydrous HCl, such as HCl gas, is cofed with 3,3,3-trifluoropropene in both gas and liquid phase reactions. The added HCl suppresses side reactions and serves as a diluent to control high heat formation. In one embodiment, the HCl is in the range of about 0.5% to about 20 mol%, in another embodiment in the range of about 1 to about 10 mol%, with respect to the amount of 1243 zf present, in another embodiment. Is present in an amount in the range of about 1.5 to about 5 mol%.

Those skilled in the art can make the best use of the present invention by using the description of the present specification without further trouble. Therefore, the specific embodiments below are to be construed as mere examples and do not constrain the disclosure of the remainder in any way.

The invention of the present application will be further described in the following non-limiting examples.

(Example 1)
5% CrCl _3- supported-chlorination of 1243zf at atmospheric pressure with acid-washed activated carbon:
2 ml of a 12-20 mesh 5% CrCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at atmospheric pressure. Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 1. The catalyst showed great activity and selectivity.

(Example 2)
5% CrCl _3- supported-chlorination of 1243zf at 25 psig (273.7 kPa) with acid-washed activated carbon:
2 ml of a 12-20 mesh 5% CrCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at 25 psig (273.7 kPa). Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 2. The catalyst showed high activity and selectivity at 25 psig (273.7 kPa).

(Example 3)
15% CrCl _3- supported-chlorination of 1243zf at atmospheric pressure with acid-washed activated carbon:
5 ml of a 12-20 mesh 15% CrCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at atmospheric pressure. Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 3. The catalyst showed great activity and selectivity.

(Example 4)
15% CrCl _3- Supported-Chlorination of 1243zf at 25 psig (273.7 kPa) with acid-washed activated carbon:
5 ml of a 12-20 mesh 15% CrCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at 25 psig (273.7 kPa). Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 4. The catalyst showed great activity and selectivity.

(Example 5)
15% CrCl _3- supported-chlorination of 1243 zf at 40 psig (377.1 kPa) with acid-washed activated carbon: 12-20 mesh 15% CrCl ₃ / C catalyst 2 ml, 1/2 inch Monel reaction It was put into the device. The catalyst was dried at 200 ° C. for 1 hour under 100 sccm N ₂ and then supplied with 1243 zf and chlorine from the top of the reactor at 40 psig (377.1 kPa). Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 5. The catalyst exhibits high activity and selectivity.

(Example 6)
5% FeCl _3- supported-chlorination of 1243zf at atmospheric pressure with acid-washed activated carbon:
2 ml of a 12-20 mesh 5% FeCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then at atmospheric pressure 1243 zf and chlorine were supplied from the top of the reactor. Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 6. The catalyst exhibits high activity and selectivity.

(Example 7)
5% FeCl _3- supported-chlorination of 1243zf at 25 psig (273.7 kPa) with acid-washed activated carbon:
2 ml of a 12-20 mesh 5% FeCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at 25 psig (273.7 kPa). Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 7. The catalyst exhibits high activity and selectivity.

(Example 8)
12.6% FeCl _3- supported-chlorination of 1243zf at atmospheric pressure with acid-cleaned activated carbon:
2 ml of a 12-20 mesh 12.6% FeCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at atmospheric pressure. Flow from the reactor was analyzed by GC and GC-MS. The results of the test are shown in 8. The catalyst exhibits high activity and selectivity.

(Example 9)
30% FeCl _3- supported-chlorination of 1243zf at atmospheric pressure with acid-washed activated carbon:
5 ml of a 12-20 mesh 30% FeCl ₃ / C catalyst was charged into a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then at atmospheric pressure 1243 zf and chlorine were supplied from the top of the reactor. Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 9. The catalyst exhibits high activity and selectivity.

(Comparative Example 1)
Chlorination of 1243zf at atmospheric pressure with acid-cleaned activated carbon:
5 ml of a 12-20 mesh carbon catalyst was placed in a 1/2 inch Monel reactor. Under 100 sccm N ₂ , the catalyst was dried at 200 ° C. for 1 hour and then supplied with 1243 zf and chlorine from the top of the reactor at atmospheric pressure. Flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 10. The catalyst exhibits high activity but lower selectivity.

FIG. 1 shows activated carbon as a catalyst (Comparative Example 1), 15% CrCl ₃ / C as a catalyst (Example 1), 15% CrCl ₃ / C as a catalyst (Example 3), and 5% FeCl ₃ / C as a catalyst (Example 3). The 243db selectivity at a temperature in the range of 60 ° C to 180 ° C and an atmospheric pressure for chlorination of 3,3,3-trifluoropropene in the gas phase reaction using Example 6) is compared. As is clearly shown, when the activated carbon is a catalyst, the selectivity of 243db begins to decrease at about 100 ° C and drops sharply at about 120 ° C, whereas the metal halide carried on the activated carbon. When is used, high selectivity is maintained even at a temperature of 160 ° C. or higher.
(Example 10)
Chlorination of 1243 zf using _{FeCl 3} as a catalyst in a liquid phase reactor:
_{3 g of FeCl 3} was charged into a 200 ml Hastelloy stirring tube (shaker tube). The reactor was evacuated, _{purged twice with N 2} and then cooled to −40 ° C. At −40 ° C., the reactor was evacuated again and 80 g (0.84 mol) of 1243 zf and 56 g (0.76 mol) of Cl ₂ were added to the reactor. While stirring, the reactor was heated to 40 ° C. and stirred at 40 ° C. for 1.5 hours. As the reaction proceeded, the pressure dropped continuously. At the end of the reaction, the pressure in the reactor dropped from 112 psig (873.5 kPa) to 7 psig (149.6 kPa). The reactor was cooled to room temperature and the liquid contents were transferred to a glass bottle containing _{50 ml of 15% Na 2} SO _{3 aqueous solution.} The organic layer was then separated from the liquid phase and 122.82 g of product was recovered. The product was analyzed by GC-MS. The data reported in Table 11 below are shown by area percent obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity of 243db was ~ 99.8%.

(Example 11)
Chlorination of 1243 zf at 50 ° C. using _{FeCl 3} as a catalyst in the liquid phase in an autoclave reactor:
A 1 liter Hastelloy autoclave was filled with _{12.4 g of anhydrous FeCl 3.} The reactor was evacuated, _{purged twice with N 2} and then cooled to −40 ° C. At −40 ° C., the reactor was evacuated again and 337 g (3.51 mol) of 1243 zf was added. Then, 1243 zf was heated to 50 ° C. with stirring. Then, 242 g (3.41 mol) of Cl ₂ was supplied at 50 ° C. for 50 minutes. After adding all Cl ₂ , the reaction was stirred for an additional hour at 50 ° C. As the reaction proceeded, the pressure dropped continuously. By the end of the reaction, the pressure in the reactor had dropped from 150 psig (1136 kPa) to 11 psig (177.2 kPa). The pressure graph of this reaction is plotted in FIG. 2 (lower plot). The _{reaction using the FeCl 3} catalyst is clearly much faster than the reactions of Comparative Examples 2 and 3 without the catalyst because the pressure drop is faster. The reactor was cooled to room temperature and the liquid contents were transferred to a glass bottle. 568 g of product was recovered and analyzed using GC-MS. The data reported in Table 12 below are shown by area percent obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity of 243db was ~ 99.8%. The _{selectivity of 243db with FeCl 3} catalyst is also higher than that of Comparative Examples 2 and 3 without catalyst.

(Comparative Example 2)
Chlorination of 1243 zf at 80 ° C. without catalyst in the liquid phase in an autoclave reactor:
A 1 liter Hastelloy autoclave was used. The reactor was evacuated, _{purged twice with N 2} and then cooled to −40 ° C. At −40 ° C., the reactor was evacuated again and 338 g (3.52 mol) of 1243 zf was added. Then, 1243 zf was heated to 80 ° C. with stirring. Then, 242 g (3.41 mol) of Cl ₂ was supplied at 80 ° C. for 119 minutes. After adding all Cl ₂ , the reaction was stirred for an additional 3.5 hours at 80 ° C. As the reaction proceeded, the pressure dropped continuously. By the end of the reaction, the pressure in the reactor had dropped from 320 psig (2308 kPa) to 40 psig (377.1 kPa). The pressure graph of this reaction is plotted in FIG. The reaction at 80 ° C. without a catalyst (Comparative Example 2, intermediate plot) has a slower pressure drop than the reaction at 50 ° C. using _{FeCl 3 in Example 11 (lower plot).} Obviously much slower. After cooling the reactor to room temperature, the liquid contents were transferred to a glass bottle containing _{100 ml of 10% Na 2} SO _{3 aqueous solution.} 568 g of product was recovered and analyzed using GC-MS. The data reported in Table 13 below are shown by area percent obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity of 243db was ~ 94.2%. The selectivity of 243db without the catalyst is lower than the selectivity of Example 11 with _{the FeCl 3 catalyst.}

(Comparative Example 3)
Chlorination of 1243 zf at 100 ° C. without catalyst in the liquid phase in an autoclave reactor:
A 1 liter Hastelloy autoclave was used. The reactor was evacuated, _{purged twice with N 2} and then cooled to −40 ° C. At −40 ° C., the reactor was evacuated again and 339 g (3.53 mol) of 1243 zf was added. Then, 1243 zf was heated to 100 ° C. with stirring. Then, 212 g (2.98 mol) of Cl ₂ was supplied at 100 ° C. for 84 minutes. After adding all Cl ₂ , the reaction was stirred for an additional 2 hours at 100 ° C. As the reaction proceeded, the pressure dropped continuously. By the end of the reaction, the pressure in the reactor had dropped from 450 psig (3204 kPa) to 264 psig (1992 kPa). The pressure graph of this reaction is plotted in FIG. 2 (upper plot). On the basis of pressure reduction, the reaction at 100 ° C. without catalyst is faster than the reaction at 80 ° C. without catalyst in Comparative Example 2, but at 50 ° C. with _{FeCl 3 catalyst in Example 11.} It is as fast as the reaction. After cooling the reactor to room temperature, the liquid contents were transferred to a glass bottle containing _{100 ml of 10% Na 2} SO _{3 aqueous solution.} 439 g of product was recovered and analyzed using GC-MS. Black tar was also found in the reactor. The data reported in Table 14 below are shown by area percent obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity of 243db was ~ 91.8%. The selectivity of 243db without the catalyst is lower than the selectivity of Example 11 with _{the FeCl 3 catalyst.}

(Comparative Example 4)
Chlorination of 1243 zf at 60 ° C. using activated carbon as a catalyst in the liquid phase in an autoclave reactor:
To a 400 ml Hastelloy stirrer tube, 3 g of activated carbon, 80 g (0.84 mol) of 1243 zf and chlorine (54 g, 0.76 mol) in the liquid phase were added. The mixture was stirred at 40 ° C. for 20 minutes. The pressure in the reactor remained at ~ 160 psig (~ 1204 kPa). Therefore, there was no sign that a reaction was occurring. The reactor was then heated to 60 ° C. and held at 60 ° C. for 90 minutes. The reaction pressure was only reduced from 236 psig (1728 kPa) to 200 psig (1480 kPa). This indicates a very slow reaction. This result indicates that activated carbon does not catalyze the chlorination of 1243 zf in the liquid phase.

Not all of the tasks described in the general description and examples above are required, some specific tasks may not be required, and one or more additional tasks are added to the above tasks. Please note that you may go. Further, the order of the list of the operations is not necessarily the order of execution.

In the present specification,% is by weight unless otherwise specified.

In the above description, the concept of the present application has been described with respect to specific embodiments. However, those skilled in the art can understand that various modifications and changes can be made without departing from the scope of the invention defined in the claims described below. Therefore, the specification of the present application should be regarded as an exemplary meaning rather than a restrictive meaning, and all such modifications are intended to be included within the scope of the present invention.

So far, the advantages and other advantages and solutions to the problems have been described in relation to the specific embodiments. However, any property that gives rise to or makes clear the advantage, advantage, solution to the problem; and any advantage, advantage, solution is decisive and mandatory within the scope of any or all claims. Or should not be construed as an essential property.

It is understood that some properties are described herein in the context of separate embodiments for clarity, but may be given in combination within a single embodiment. Should. Conversely, the various properties are described in a single embodiment for brevity, but may be given as separate or arbitrary subcombinations.

Claims (42)

The process of preparing 2,3,3,3-tetrafluoropropene, in which chlorine is brought into contact with 3,3,3-trifluoropropene in the presence of a catalyst, 1,1,1- With the process of forming trifluoro-2,3-dichloropropane
The process of dehydrochlorinating at least a part of 1,1,1-trifluoro-2,3-dichloropropane to form 2-chloro-3,3,3-trifluoropropene, and
Including the step of converting at least a part of 2-chloro-3,3,3-trifluoropropene to 2,3,3,3-tetrafluoropropene.
The catalyst comprises at least one metal halide, the metal being selected from nickel, iron, chromium and combinations thereof .
The contact step is carried out in the gas phase
At least one metal halide is supported on the activated carbon,
A process characterized by that. The process according to claim 1, wherein the activated carbon is acid-washed or caustic-washed. The process according to claim 1, wherein the halide is a chloride. The process according to claim 1 , wherein the metal halide is nickel chloride, iron chloride, or chromium chloride. The contact step has a molar ratio of 3,3,3-trifluoropropene to chlorine gas at temperatures in the range of 80 ° C to 200 ° C and pressures in the range of 10 psig (170.3 kPa) to 100 psig (790.8 kPa). The process according to claim 1, wherein the process is performed in a ratio of 1: 0.02 to 1: 1. The process of claim 5 , wherein the temperature is in the range of 80 ° C to 160 ° C. The process of claim 6 , wherein the temperature is in the range of 80 ° C to 130 ° C. The process of claim 5 , wherein the pressure is in the range of 1 atmosphere (101.3 kPa) to 50 psig (446.1 kPa). The process of claim 5 , wherein the pressure is in the range of 10 psig (170.3 kPa) to 50 psig (446.1 kPa). The process of claim 5 , wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is in the range 1: 0.1 to 1: 0.8. The process of claim 10 , wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is in the range 1: 0.1 to 1: 0.5. The process of claim 10 , wherein the temperature is in the range of 80 ° C to 160 ° C. The process of claim 10 , wherein the temperature is in the range of 80 ° C to 130 ° C. The process of claim 10 , wherein the pressure is in the range of 1 atmosphere (101.3 kPa) to 50 psig (446.1 kPa). The process of claim 10 , wherein the pressure is in the range of 10 psig (170.3 kPa) to 50 psig (446.1 kPa). 11. The process of claim 11 , wherein the temperature is in the range of 80 ° C to 160 ° C. 11. The process of claim 11 , wherein the temperature is in the range of 80 ° C to 130 ° C. 11. The process of claim 11 , wherein the pressure is in the range of 1 atmosphere (101.3 kPa) to 50 psig (446.1 kPa). 11. The process of claim 11 , wherein the pressure is in the range of 10 psig (170.3 kPa) to 50 psig (446.1 kPa). The process of claim 1, wherein the chlorine is _{obtained by the reaction of HCl with O 2.} The process of claim 1, wherein the contact time is in the range of 0.1 seconds to 2 minutes. 21. The process of claim 21, wherein the contact time is in the range of 5 seconds to 1 minute. The process of preparing 2,3,3,3-tetrafluoropropene, which is a process
In the presence of an effective amount of catalyst, chlorine is brought into contact with 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane.
The process of dehydrochlorinating at least a part of 1,1,1-trifluoro-2,3-dichloropropane to form 2-chloro-3,3,3-trifluoropropene, and
Including the step of adding at least a part of 2-chloro-3,3,3-trifluoropropene to 2,3,3,3-tetrafluoropropene.
The catalyst comprises at least one metal halide, the metal being selected from nickel, iron, chromium and combinations thereof .
The contact step is carried out in the liquid phase and
The process, wherein the catalytically effective amount varies from 0.1% to 10% by weight of the total amount of reactants present. 23. The process of claim 23 , wherein the halide is chloride. 23. The process of claim 23 , wherein the metal halide is nickel chloride, iron chloride, or chromium chloride. 23. The process of claim 23 , wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is 1: 0.02 to 1: 1. 23. The process of claim 23 , wherein the process is carried out at a temperature in the range of 30 ° C to 110 ° C. 24. The process of claim 24 , wherein the process is performed at a temperature in the range of 35 ° C to 90 ° C. 26. The process of claim 26 , wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is 1: 0.1 to 1: 0.95. 26. The process of claim 26 , wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is 1: 0.1 to 1: 0.9. 29. The process of claim 29 , wherein the process is performed at a temperature in the range of 30 ° C to 110 ° C. 29. The process of claim 29 , wherein the process is performed at a temperature in the range of 35 ° C to 90 ° C. 30. The process of claim 30 , wherein the process is performed at a temperature in the range of 30 ° C to 110 ° C. 30. The process of claim 30 , wherein the process is performed at a temperature in the range of 35 ° C to 90 ° C. The chlorine comes into contact with 3,3,3-trifluoropropene in the solvent in the presence of a metal halide, and the solvent is carbon tetrachloride, 1,1,2-trichloro-1,2. , 2-trifluoroethane, CF ₃ (CF ₂ ) _{n C 5-8} linear perfluoroalkyl compound represented by CF ₃ (where n is an integer of 3 to 6 including both ends), or hexachloroacetone. 31. The process of claim 31. The chlorine comes into contact with 3,3,3-trifluoropropene in the solvent in the presence of a metal halide, and the solvent is carbon tetrachloride, 1,1,2-trichloro-1,2,2-. Trifluoroethane, CF ₃ (CF ₂ ) _{n C 5-8} linear perfluoroalkyl compound represented by CF ₃ (where n is an integer of 3 to 6 including both ends), or hexachloroacetone. The process of claim 32 , characterized in that. The process according to claim 1 or 23 , wherein HCl is co-supplied with 3,3,3-trifluoropropene or chlorine. 37. The process of claim 37 , wherein the HCl is anhydrous. 38. The process of claim 38 , wherein said HCl is present in 0.5% to 20 mol% relative to the mol% of 3,3,3-trifluoropropene present. 23. The process of claim 23 , wherein the catalytically effective amount varies from 0.5% to 6% by weight of the total amount of reactants present. 23. The process of claim 23 , wherein the catalytically effective amount varies from 1% to 4% by weight of the total amount of reactants present. 23. The process of claim 23, 29 or 30, characterized in that it is carried out at temperatures varying from 20 ° C to 200 ° C.

Images